Flame retardant fillers prepared from bridged polysilsesquioxanes

ABSTRACT

A bridged polysilsesquioxane-based flame retardant filler imparts flame retardancy to manufactured articles such as printed circuit boards (PCBs), connectors, and other articles of manufacture that employ thermosetting plastics or thermoplastics. In an exemplary synthetic method, a bridged polysilsesquioxane-based flame retardant filler is prepared by sol-gel polymerization of a monomer having two or more trialkoxysilyl groups attached to an organic bridging group that contains a fire retardant group (e.g., a halogen atom, a phosphinate, a phosphonate, a phosphate ester, and combinations thereof). Bridged polysilsesquioxane particles formed by sol-gel polymerization of (((2,5-dibromo-1,4-phenylene)bis(oxy))bis(ethane-2,1-diyl))bis(trimethoxysilane), for example, and follow-on sol-gel processing may serve both as a filler for rheology control (viscosity, flow, etc.) and a flame retardant. In an exemplary application, a PCB laminate stack-up includes conductive planes separated from each other by a dielectric material that includes a bridged polysilsesquioxane-based flame retardant filler.

BACKGROUND OF THE INVENTION

1. Field of Invention

The present invention relates in general to the field of flameretardancy. More particularly, the present invention relates to usingflame retardant fillers prepared from bridged polysilsesquioxanes toimpart flame retardancy to manufactured articles such as printed circuitboards (PCBs), connectors, and other articles of manufacture that employthermosetting plastics or thermoplastics.

2. Background Art

In the manufacture of PCBs, connectors, and other articles ofmanufacture that employ thermosetting plastics (also known as“thermosets”) or thermoplastics, incorporation of a filler material aswell as a flame retardant is required for rheology control (viscosity,flow, etc.) and ignition resistance, respectively. Typically, bothattributes are not found in one material. That is, silica particles aregenerally the filler of choice for rheology control, whereas brominatedorganic compounds impart flame retardancy. Consequently, the basematerial (e.g., epoxy resin for PCBs, and liquid crystal polymer (LCP)for connectors) properties are compromised because a relatively largequantity of both a filler and a flame retardant is necessary to achievethe desired properties.

Therefore, a need exists for an improved mechanism for imparting flameretardancy to manufactured articles such as PCBs, connectors, and otherarticles of manufacture that employ thermoplastics or thermosets.

SUMMARY OF THE INVENTION

In accordance with some embodiments of the present invention, a bridgedpolysilsesquioxane-based flame retardant filler imparts flame retardancyto manufactured articles such as printed circuit boards (PCBs),connectors, and other articles of manufacture that employ thermosettingplastics or thermoplastics. In an exemplary synthetic method, a bridgedpolysilsesquioxane-based flame retardant filler is prepared by sol-gelpolymerization of a monomer having two or more trialkoxysilyl groupsattached to an organic bridging group that contains a fire retardantgroup (e.g., a halogen atom, a phosphinate, a phosphonate, a phosphateester, and combinations thereof). Bridged polysilsesquioxane particlesformed by sol-gel polymerization of(((2,5-dibromo-1,4-phenylene)bis(oxy))-bis(ethane-2,1-diyl))bis(trimethoxysilane),for example, and follow-on sol-gel processing may serve both as a fillerfor rheology control (viscosity, flow, etc.) and a flame retardant. Inan exemplary application, a PCB laminate stack-up includes conductiveplanes separated from each other by a dielectric material that includesa bridged polysilsesquioxane-based flame retardant filler.

BRIEF DESCRIPTION OF THE DRAWINGS

The preferred exemplary embodiments of the present invention willhereinafter be described in conjunction with the appended drawings,where like designations denote like elements.

FIG. 1 is a block diagram illustrating an exemplary printed circuitboard (PCB) having layers of dielectric material that incorporate abridged polysilsesquioxane-based flame retardant filler in accordancewith some embodiments of the present invention.

FIG. 2 is a block diagram illustrating an exemplary laminate stack-up ofthe PCB shown in FIG. 1.

FIG. 3 is a block diagram illustrating an exemplary connector having aplastic housing that incorporates a bridged polysilsesquioxane-basedflame retardant filler in accordance with some embodiments of thepresent invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In accordance with some embodiments of the present invention, a bridgedpolysilsesquioxane-based flame retardant filler imparts flame retardancyto manufactured articles such as printed circuit boards (PCBs),connectors, and other articles of manufacture that employ thermosettingplastics or thermoplastics. In an exemplary synthetic method, a bridgedpolysilsesquioxane-based flame retardant filler is prepared by sol-gelpolymerization of a monomer having two or more trialkoxysilyl groupsattached to an organic bridging group that contains a fire retardantgroup (e.g., a halogen atom, a phosphinate, a phosphonate, a phosphateester, and combinations thereof). Bridged polysilsesquioxane particlesformed by sol-gel polymerization of(((2,5-dibromo-1,4-phenylene)bis(oxy))-bis(ethane-2,1-diyl))bis(trimethoxysilane),for example, and follow-on sol-gel processing may serve both as a fillerfor rheology control (viscosity, flow, etc.) and a flame retardant.

An exemplary printed circuit board (PCB) implementation of the presentinvention is described below with reference to FIGS. 1 and 2, while anexemplary connector implementation of the present invention is describedbelow with reference to FIG. 3. However, those skilled in the art willappreciate that the present invention applies equally to anymanufactured article that employs thermosetting plastics (also known as“thermosets”) or thermoplastics.

As described below, a bridged polysilsesquioxane in accordance with someembodiments of the present invention may be synthesized by, for example,preparing a halogen-containing silane monomer having two or moretrialkoxysilyl groups attached to an organic bridging group thatcontains a halogen-based fire retardant group such as one or morebromine atoms, and then reacting the halogen-containing silane monomervia sol-gel polymerization. This first pathway to prepare a bridgedpolysilsesquioxane in accordance with some embodiments of the presentinvention is exemplified by reaction schemes 1 and 2, below.

However, those skilled in the art will appreciate that a bridgedpolysilsesquioxane in accordance with some embodiments of presentinvention may be synthesized using other processes and reaction schemes.For example, a bridged polysilsesquioxane in accordance with someembodiments of the present invention may be synthesized by, for example,preparing a phosphorous-containing silane monomer having two or moretrialkoxysilyl groups attached to an organic bridging group thatcontains a phosphorous-based flame retardant group such as aphosphinate, and then reacting the phosphorous-containing silane monomervia sol-gel polymerization. This second pathway to prepare a bridgedpolysilsesquioxane in accordance with some embodiments of the presentinvention is exemplified by reaction scheme 3, below.

Once the sol-gel polymerization reaction of either the first or secondpathway is complete, conventional follow-on sol-gel processing may beused to produce bridged polysilsesquioxane particles in accordance withsome embodiments of the present invention. These particles may serveboth as a filler for rheology control (viscosity, flow, etc.) and aflame retardant. Typically, the organic-based solvent used in thesol-gel polymerization reaction is removed after the sol-gelpolymerization reaction is complete. The gel is then dried, and crushedinto particles. In terms of size, the bridged polysilsesquioxaneparticles may be course particles, fine particles, ultrafine particles,or nanoparticles.

The first pathway entails synthesizing brominated silane precursors thatcan be polymerized, via sol-gel chemistry, to form bridgedpolysilsesquioxanes. The polysilsesquioxanes are modified with a veryhigh level of bromine and function as both rheology modifiers and flameretardants.

The first pathway is exemplified below in two non-limiting reactionschemes (i.e., reaction schemes 1 and 2). A reaction scheme (reactionscheme 1) follows for synthesizing a bridged polysilsesquioxane (thirdstep of reaction scheme 1) through an intermediate synthesis of avinyl-functionalized substituted monomer by reacting2,5-dibromohydroquinone and allyl chloride (first step of reactionscheme 1) and then, in turn, an intermediate synthesis of a substitutedsilane monomer by reacting the vinyl-functionalized substituted monomerand trimethoxysilane (second step of reaction scheme 1) in accordancewith some embodiments of the present invention. Hence, reaction scheme 1has three steps. In the first step of the first reaction scheme,2,5-dibromohydroquinone is reacted with allyl chloride in the presenceof triethylamine to form 1,4-bis(allyloxy)-2,5-dibromobenzene. Thiscompound is subsequently reacted with trimethoxysilane in the secondstep of the first reaction scheme in the presence of a Pt catalyst toform the substituted silane monomer,(((2,5-dibromo-1,4-phenylene)bis(oxy))bis(ethane-2,1-diyl))bis(trimethoxysilane).This substituted silane monomer then undergoes sol-gel polymerization inthe third step of the first reaction scheme and subsequently undergoesconventional sol-gel processing to form bridged polysilsesquioxaneparticles.

The first step of reaction scheme 1 is performed at room temperatureusing conventional procedures well known to those skilled in the art. Inthis first step, 2,5-dibromohydroquinone is reacted with allyl chloridein the presence of triethylamine to form1,4-bis(allyloxy)-2,5-dibromobenzene. Generally, stoichiometricquantities of the reactants may be used. Triethylamine is the solvent.

The second step of reaction scheme 1 is performed at room temperatureusing conventional procedures well known in the art. In this secondstep, 1,4-bis(allyloxy)-2,5-dibromobenzene is reacted withtrimethoxysilane in the presence of a Pt catalyst to form thesubstituted silane monomer,(((2,5-dibromo-1,4-phenylene)bis(oxy))bis(ethane-2,1-diyl))bis(trimethoxysilane).Generally, stoichiometric quantities of the reactants may be used. Thereaction is performed in the presence of a hydrosilylation catalyst suchas Karstedt's catalyst(Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution)or other catalyst known to those skilled in the art within a suitablesolvent such as toluene or other solvent known to those skilled in theart to dissolve the hydrosilylation catalyst. The hydrosilylationcatalyst used is typically a Pt catalyst. The preferred Pt catalyst isKarstedt's catalyst. However, one skilled in the art will appreciatethat any of a number of other catalysts may be used. For example,[Cp*Ru(MeCN)₃]PF₆ (available from Sigma-Aldrich, St. Louis, Mo.) is ahydrosilylation catalyst that may be utilized in the second step ofreaction scheme 1. Using [Cp*Ru(MeCN)₃]PF₆ catalyst, 2-5 mol % catalystis typically used in acetone at room temperature.

Trimethoxysilane is a commercially available, conventionalhydrogen-terminated silane coupling agent. Typically, a coupling agentis used to join two disparate surfaces. In the manufacture of printedcircuit boards (PCBs), a silane coupling agent is often used to join avarnish coating (e.g., an epoxy-based resin) to a substrate (e.g., glasscloth) to define a laminate, or laminated structure. The silane couplingagent typically consists of an organofunctional group to bind to thevarnish coating and a hydrolyzable group that binds to the surface ofthe substrate. In particular, the alkoxy groups on the silicon hydrolyzeto silanols, either through the addition of water or from residual wateron the surface of the substrate. Subsequently, the silanols react withhydroxyl groups on the surface of the substrate to form a siloxane bond(Si-O-Si) and eliminate water.

The third step of reaction scheme 1 is performed at room temperatureusing conventional procedures well known in the art. In this third step,the substituted silane monomer,(((2,5-dibromo-1,4-phenylene)bis(oxy))bis(ethane-2,1-diyl))bis(trimethoxysilane),undergoes sol-gel polymerization to form a bridged polysilsesquioxane.The substituted silane monomer may be purified by fractionaldistillation prior to sol-gel polymerization. Generally, purification ispreferred but not necessary.

Sol-gel polymerization techniques are well known in the art. Forexample, U.S. Pat. No. 5,371,154, issued Dec. 6, 1994 to Brandvold etal., entitled “PROCESS FOR FORMING ACID FUNCTIONALIZEDORGANICALLY-BRIDGED POLYSILSESQUIOXANES”, discloses sol-gel processingtechniques in the context of a process for forming a solid acidcatalyst. The process disclosed in the Brandvold et al. patent involvespolymerizing a monomer through sol-gel processing to form anorganically-bridged polysilsesquioxane, reacting an acid group onto theorganic portion of the organically bridged polysilsesquioxane, andrecovering the acid functionalized product. The Brandvold et al. patentis hereby incorporated herein by reference in its entirety.

Generally, sol-gel polymerization techniques are characterized by: 1)hydrolysis of monomers to silanols; and 2) condensation of the silanolsto form siloxanes, first as a colloidal solution (sol), and thereafterwith continued condensation accompanied by extensive branching andcross-linking, to form an integrated network (gel), i.e., a solid,amorphous, three-dimensional network of siloxane linkages havingorganically bridged silicon atoms (i.e., bridged polysilsesquioxanes),where the network is supported by a solvent. Hence, sol-gelpolymerization is a wet-chemical technique in which a sol graduallyevolves to form a gel-like diphasic system containing both a liquidphase and a solid phase.

Generally, water is the solvent of choice in sol-gel polymerizationtechniques. The choice of solvent is not critical as long as the monomeris soluble in the solvent, and the solvent is at least partiallymiscible with water. Acceptable solvents include, but are not limitedto, alcohols, ethers and polar aprotic solvents. The following solventsare the most common: ethanol, methanol, isopropyl alcohol,tetrahydrofuran, dimethylformamide, and acetonitrile. Furthermore,various other hydrocarbon solvents in which the monomer is miscible maybe used as cosolvents. One example of such a cosolvent is benzene. Whichsolvent is preferred depends on the solubility of the subject monomer.In many cases, the preferred solvents are tetrahydrofuran, methanol,ethanol, and mixtures thereof. In the third step of reaction scheme 1,the exemplary solvent is methanol.

In addition, one or more surfactants may be used in the sol-gelpolymerization. Typically, a surfactant is added to the solvent in orderto moderate the sol/gel transition, i.e., formation of the gel network.Suitable surfactants include, but are not limited to, sodium dodecylsulfate (SDS) and cetyltrimethylammonium bromide (CTAB). The surfactantswould be used at concentrations below their critical micelleconcentration (CMC), i.e., 0.0082 M for SDS and 0.001 M for CTAB, bothat 25° C. In the third step of reaction scheme 1, the exemplarysurfactant may be SDS.

Initially, the substituted silane monomer,(((2,5-dibromo-1,4-phenylene)bis(oxy))bis(ethane-2,1-diyl))bis(trimethoxysilane),is solubilized in a suitable solvent. As noted above, the solvent mayalso contain a suitable surfactant. Then, the solution is treated withat least a three molar equivalent of water in the presence of an acid orbase to catalyze the sol-gel polymerization reaction. The methoxysilanesof the monomer are hydrolyzed to silanols which then condense witheither other silanols or methoxysilanes to generate siloxane bonds. Thehydrolysis and condensation reactions may require from less than 1 to 48hours at room temperature. The choice of base is not critical to thesuccess of the sol-gel polymerization, and the most common base isaqueous ammonia at concentrations as low as 5.0 mol % to as high as 570mol %. Similarly, when acid is employed, the choice of acid is notcritical to the success of the sol-gel polymerization reaction andtypically mineral acid is used, the most frequent being aqueoushydrochloric acid at a concentrations as low as 0.5 mol % or as high as10.8 mol %. In the third step of reaction scheme 1, the exemplary baseis potassium hydroxide.

The bridged polysilsesquioxane synthesized in the third step of reactionscheme 1 subsequently undergoes conventional sol-gel processing to formbridged polysilsesquioxane particles. Typically, the organic-basedsolvent used in the sol-gel polymerization reaction is removed after thesol-gel polymerization reaction is complete. The gel is then dried, andcrushed into particles. In terms of size, the bridged polysilsesquioxaneparticles may be course particles, fine particles, ultrafine particles,or nanoparticles.

After the hydrolysis and condensation reactions are complete (i.e., thesol-gel polymerization is complete), and the gel has formed and curedfor at least forty-eight hours, the solvent typically must be removed.Solvent may be removed by supercritical drying, solvent extraction, orsimply breaking up the gel and washing with water. Supercritical dryingis accomplished by placing the wet gel in an autoclave to dry using CO₂at supercritical conditions of 50° C. and 2000 psig for 6 to 24 hours.When the drying is accomplished under these supercritical conditions,there is no liquid vapor interface to develop strain and the dried gelshows little fracturing.

Solvent extraction is a multistep procedure which requires thesuccessive treatment of the wet gel with solvents of decreasingdielectric constant. For example, if tetrahydrofuran was used in theprocessing, the tetrahydrofuran could be replaced directly with ether.On the other hand, if methanol was used in the processing (e.g., thethird step of reaction scheme 1), the methanol must be first exchangedwith tetrahydrofuran, and then the tetrahydrofuran is replaced withether. To perform the solvent exchange, the gel is placed in a finefritted glass funnel containing twice the gel volume of the solvent usedin the sol-gel polymerization reaction. Then the gel is washed with thenext solvent in the same manner, continuing until the last solventpassed over the gel is ether.

Also the wet gel can simply be broken up and washed with water to removethe solvent. This procedure typically is utilized only when the degreeof fracturing in the gel is not a concern.

After the solvent is removed, the gel is then dried under vacuum fortwenty-four hours at room temperature. The gel may now be crushed intoparticles, and re-dried under vacuum. The resultant particles may becourse particles, fine particles, ultrafine particles, or nanoparticles.

Those skilled in the art will appreciate that the various steps ofreaction scheme 1 are set forth for the purpose of illustration notlimitation. For example, the first step of reaction scheme 1 synthesizesa particular vinyl-functionalized substituted monomer,1,4-bis(allyloxy)-2,5-dibromobenzene, by reacting2,5-dibromohydroquinone and allyl chloride in the presence oftriethylamine. This particular synthesis of this particularvinyl-functionalized substituted monomer is exemplary. Any suitablevinyl-functionalized substituted monomers may be synthesized in lieu of1,4-bis(allyloxy)-2,5-dibromobenzene. The vinyl-functionalizedTBBPA-based monomer synthesized in the first step of reaction scheme 2is an example of another suitable vinyl-substituted monomer. In general,suitable vinyl-functionalized substituted monomers in accordance withsome embodiments of the first pathway include any organic monomer thatis vinyl-functionalized in at least two sites (e.g., hydroquinone-basedmonomers, bisphenol A-based monomers) and substituted with one or morehalogen atoms.

The second step of reaction scheme 1 synthesizes a particularsubstituted silane monomer,(((2,5-dibromo-1,4-phenylene)bis(oxy))bis(ethane-2,1-diyl))bis(trimethoxysilane),by reacting 1,4-bis(allyloxy)-2,5-dibromobenzene with trimethoxysilanein the presence of a Pt catalyst. This particular synthesis of thisparticular substituted silane monomer is exemplary. Any suitablesubstituted silane monomer may be synthesized in lieu of(((2,5-dibromo-1,4-phenylene)bis(oxy))bis(ethane-2,1-diyl))bis(trimethoxysilane).The substituted silane monomer synthesized in the second step ofreaction scheme 2 is an example of another suitable substituted silanemonomer. In general, suitable substituted silane monomers in accordancewith some embodiments of the first pathway include two or moretrialkoxysilyl groups attached to an organic bridging group thatcontains a halogen based flame retardant. Typically, the organicbridging group has a backbone portion that includes at least two oxygenatoms. Those skilled in the art will appreciate that such a monomer maybe synthesized by reacting any suitably functionalized substitutedmonomer (e.g., a halogen based flame retardant functionalized to containa suitable functional group) with any suitable silane coupling agent. Ingeneral, suitable functional groups may include vinyl, isocyanate,amine, and epoxy functional groups. In general, suitable silane couplingagents include conventional hydrogen-terminated silanes, such astrimethoxysilane and triethoxysilane, and conventional vinyl-terminatedsilanes, such as vinyltrimethoxysilane and vinyltriethoxysilane.

A hydrogen-terminated silane, such as trimethoxysilane, may be used inthe second step of reaction scheme 1 to synthesize the substitutedsilane monomer by hydrosilylation catalyzed coupling. As noted above,trimethoxysilane is a commercially available, conventionalhydrogen-terminated silane coupling agent. The substituted silanemonomer is synthesized in the second step of reaction scheme 1 byhydrosilylation catalyzed coupling of the hydrogen-terminated silaneonto the vinyl-functionalized substituted monomer (which is synthesizedin the first step of reaction scheme 1). Alternatively, avinyl-terminated silane, such as vinyltrimethoxysilane, may be used inthe second step of reaction scheme 1 to synthesize the substitutedsilane monomer by olefin metathesis catalyzed coupling. In thisalternative case, the substituted silane monomer is synthesized byolefin metathesis catalyzed coupling of the vinyl-terminated silane ontothe vinyl-functionalized substituted monomer (which is synthesized inthe first step of reaction scheme 1). This reaction is performed in thepresence of an olefin metathesis catalyst such as Grubbs' catalyst(first generation (G1) and/or second generation (G2)), Schrockakylidenes, or other catalysts known to those skilled in the art withina suitable solvent such as dichloromethane (DCM) or other solvent knownto those skilled in the art to dissolve the olefin catalyst. Generally,stoichiometric quantities of reactants may be used. This reaction isperformed at room temperature using conventional procedures well knownin the art.

A reaction scheme (reaction scheme 2) follows for synthesizing a bridgedpolysilsesquioxane (third step of reaction scheme 2) through anintermediate synthesis of a vinyl-functionalized substituted monomer byreacting TBBPA and allyl bromide (first step of reaction scheme 2) andthen, in turn, an intermediate synthesis of a substituted silane monomerby reacting the vinyl-functionalized substituted monomer andtrimethoxysilane (second step of reaction scheme 2) in accordance withsome embodiments of the present invention. Hence, reaction scheme 2 hasthree steps. In the first step of the second reaction scheme,tetrabromobisphenol A (TBBPA) is reacted with allyl bromide in thepresence of sodium hydroxide (NaOH) and tetrahydrofuran (THF) to formthe vinyl-functionalized substituted monomer. This compound issubsequently reacted in the second step of the second reaction scheme inthe presence of a Pt catalyst to form the substituted silane monomer.This substituted silane monomer then undergoes sol-gel polymerization inthe third step of the second reaction scheme and in subsequent sol-gelprocessing to form bridged polysilsesquioxane particles.

The first step of reaction scheme 2 is performed at room temperatureusing conventional procedures well known to those skilled in the art. Inthis first step, tetrabromobisphenol A (TBBPA) is reacted with allylbromide in the presence of sodium hydroxide (NaOH) and tetrahydrofuran(THF) to form the vinyl-functionalized substituted monomer. Generally,stoichiometric quantities of the reactants may be used. THF is thesolvent. Potassium hydroxide (KOH) may be used in lieu of NaOH. Both aretypically used in the 1M concentration range, but more specifically, thereaction requires six equivalents of alkaline water for each bridgedsilsesquioxane molecule.

The second and third steps of reaction scheme 2 respectively correspondto the second and third steps of reaction scheme 1, described above.

The bridged polysilsesquioxane synthesized in the third step of reactionscheme 2 subsequently undergoes conventional sol-gel processing to formbridged polysilsesquioxane particles. Suitable conventional sol-gelprocessing is described above with respect to reaction scheme 1.

The second pathway is exemplified below in another non-limiting reactionscheme (i.e., reaction scheme 3). A reaction scheme (reaction scheme 3)follows for synthesizing a bridged polysilsesquioxane (second step ofreaction scheme 3) through an intermediate synthesis of aphosphorous-containing silane monomer by reacting a vinyl-functionalizedphosphorous-containing monomer and trimethoxysilane (first step ofreaction scheme 3) in accordance with some embodiments of the presentinvention. Hence, reaction scheme 3 has two steps. In the first step ofthe third reaction scheme, ethyl divinyl phosphinate is reacted withtrimethoxysilane in the presence of a Pt catalyst to form aphosphorous-containing silane monomer. This phosphorous-containingsilane monomer then undergoes sol-gel polymerization in the second stepof the third reaction scheme and subsequently undergoes conventionalsol-gel processing to form bridged polysilsesquioxane particles.

The first step of reaction scheme 3 is performed at room temperatureusing conventional procedures well known in the art. In this first step,ethyl divinyl phosphinate is reacted with trimethoxysilane in thepresence of a Pt catalyst to form the phosphorous-containing silanemonomer. Generally, stoichiometric quantities of the reactants may beused. The reaction is performed in the presence of a hydrosilylationcatalyst such as Karstedt's catalyst(Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution)or other catalyst known to those skilled in the art within a suitablesolvent such as toluene or other solvent known to those skilled in theart to dissolve the hydrosilylation catalyst. The hydrosilylationcatalyst used is typically a Pt catalyst. The preferred Pt catalyst isKarstedt's catalyst. However, one skilled in the art will appreciatethat any of a number of other catalysts may be used. For example,[Cp*Ru(MeCN)₃]PF₆ (available from Sigma-Aldrich, St. Louis, Mo.) is ahydrosilylation catalyst that may be utilized in the second step ofreaction scheme 1. Using [Cp*Ru(MeCN)₃]PF₆ catalyst, 2-5 mol % catalystis typically used in acetone at room temperature.

Ethyl divinyl phosphinate (CAS Number 30594-15-1), which is alsoreferred to as phosphonic acid, diethenyl-, ethyl ester, is acommercially available conventional phosphorous-based flame retardant.Trimethoxysilane is a commercially available, conventionalhydrogen-terminated silane coupling agent.

The second step of reaction scheme 3 is performed at room temperatureusing conventional procedures well known in the art. In this secondstep, the phosphorous-containing silane monomer undergoes sol-gelpolymerization to form a bridged polysilsesquioxane. The second step ofreaction scheme 3 corresponds to the third step of reaction scheme 1,described above.

The bridged polysilsesquioxane synthesized in the second step ofreaction scheme 3 subsequently undergoes conventional sol-gel processingto form bridged polysilsesquioxane particles. Suitable conventionalsol-gel processing is described above with respect to reaction scheme 1.Typically, the solvent used in the sol-gel polymerization reaction isremoved after the sol-gel polymerization reaction is complete. The gelis then dried, and crushed into particles. In terms of size, the bridgedpolysilsesquioxane particles may be course particles, fine particles,ultrafine particles, or nanoparticles.

Those skilled in the art will appreciate that the various steps ofreaction scheme 3 are set forth for the purpose of illustration notlimitation. For example, the first step of reaction scheme 3 utilizes asa reactant a particular vinyl-functionalized phosphorous-containingmonomer, ethyl divinyl phosphinate. This utilization of this particularvinyl-functionalized phosphorous-containing monomer is exemplary. Anysuitable vinyl-functionalized phosphorous-containing monomer may beutilized in lieu of ethyl divinyl phosphinate. In general, suitablevinyl-functionalized phosphorous-containing monomers in accordance withsome embodiments of the second pathway include anyphosphorous-containing organic monomer that is vinyl-functionalized inat least two sites.

Ethyl diallyl phosphinate and propyl diallyl phosphinate are examples ofother suitable vinyl-functionalized phosphorous-containing monomers.Ethyl diallyl phosphinate (CAS Number 757-71-1), which is also referredto as phosphonic acid, diallyl-, ethyl ester, is a commerciallyavailable conventional phosphorous-based flame retardant. Propyl diallylphosphinate (CAS Number 665-69-0), which is also referred to asphosphonic acid, diallyl-, propyl ester, is a commercially availableconventional phosphorous-based flame retardant.

The first step of reaction scheme 3 synthesizes a particularphosphorous-containing silane monomer by reacting ethyl divinylphosphinate with trimethoxysilane in the presence of a Pt catalyst. Thisparticular synthesis of this particular phosphorous-containing silanemonomer is exemplary. Any suitable phosphorous-containing silane monomermay be synthesized in lieu of this particular one. In general, suitablephosphorous-containing silane monomers in accordance with someembodiments of the second pathway include two or more trialkoxysilylgroups attached to an organic bridging group that contains aphosphorous-based flame retardant. Those skilled in the art willappreciate that such a monomer may be synthesized by reacting anysuitably functionalized phosphorous-containing monomer (e.g., aphosphorous-based flame retardant functionalized to contain a suitablefunctional group) with any suitable silane coupling agent. In general,suitable functional groups may include vinyl, isocyanate, amine, andepoxy functional groups. In general, suitable silane coupling agentsinclude conventional hydrogen-terminated silanes, such astrimethoxysilane and triethoxysilane, and conventional vinyl-terminatedsilanes, such as vinyltrimethoxysilane and vinyltriethoxysilane.

A hydrogen-terminated silane, such as trimethoxysilane, may be used inthe first step of reaction scheme 3 to synthesize thephosphorous-containing silane monomer by hydrosilylation catalyzedcoupling. As noted above, trimethoxysilane is a commercially available,conventional hydrogen-terminated silane coupling agent. Thephosphorous-containing silane monomer is synthesized in the first stepof reaction scheme 3 by hydrosilylation catalyzed coupling of thehydrogen-terminated silane onto the vinyl-functionalizedphosphorous-containing monomer. Alternatively, a vinyl-terminatedsilane, such as vinyltrimethoxysilane, may be used in the first step ofreaction scheme 3 to synthesize the phosphorous-containing silanemonomer by olefin metathesis catalyzed coupling. In this alternativecase, the phosphorous-containing silane monomer is synthesized by olefinmetathesis catalyzed coupling of the vinyl-terminated silane onto thevinyl-functionalized phosphorous-containing monomer. This reaction isperformed in the presence of an olefin metathesis catalyst such asGrubbs' catalyst (first generation (G1) and/or second generation (G2)),Schrock akylidenes, or other catalysts known to those skilled in the artwithin a suitable solvent such as dichloromethane (DCM) or other solventknown to those skilled in the art to dissolve the olefin catalyst.Generally, stoichiometric quantities of reactants may be used. Thisreaction is performed at room temperature using conventional procedureswell known in the art.

Functionalized phosphorous-containing monomers suitable for reactingwith silane coupling agents to produce phosphorous-containing silanemonomers in accordance with some embodiments of the present inventionmay be either obtained commercially or synthesized. For example,suitable functionalized phosphorous-containing monomers that may beobtained commercially include dimethyl vinylphosphonate, dimethylallylphosphonate, diethyl vinylphosphonate, and diethylallylphosphonate. Generally, suitable functionalizedphosphorous-containing monomers may be synthesized by functionalizing aconventional phosphorous-based flame retardant, such as a phosphonate(e.g., dimethyl methyl phosphonate; diethyl ethyl phosphonate; dimethylpropyl phosphonate; diethyl N,N-bis(2-hydroxyethyl)amino methylphosphonate; phosphonic acid,methyl(5-methyl-2-methyl-1,3,2-dioxaphosphorinan-5-y)ester,P,P′-dioxide; and phosphonic acid,methyl(5-methyl-2-methyl-1,3,2-dioxaphosphorinan-5-yl)methyl, methylester, P-oxide), a phosphate ester (e.g., triethyl phosphate; tributylphosphate; trioctyl phosphate; and tributoxyethyl phosphate), or aphosphinate.

A conventional phosphorous-based flame retardant typically includes oneor more of a phosphonate, a phosphate ester, or a phosphinate.Conventional phosphorous-based flame retardants that are phosphonateshave the following generic molecular structure:

where R₁, R₂ and R₃ are organic substituents (e.g., alkyl, aryl, etc.)that may be the same or different.

Conventional phosphorous-based flame retardants that are phosphateesters have the following generic molecular structure:

where R₁, R₂ and R₃ are organic substituents (e.g., alkyl, aryl, etc.)that may be the same or different.

Conventional phosphorous-based flame retardants that are phosphinateshave the following generic molecular structure:

where R₁, R₂ and R₃ are organic substituents (e.g., alkyl, aryl, etc.)that may be the same or different.

One or more of the above conventional phosphorous-based flame retardants(i.e., phosphonate, phosphate ester, and/or phosphinate) and/or otherconventional phosphate-based flame retardants may be functionalizedusing procedures well known to those skilled in the art to producefunctionalized phosphorous-containing monomers suitable for reactingwith silane coupling agents in accordance with some embodiments of thepresent invention.

For example, a conventional phosphorous-based flame retardant that is aphosphinate may be functionalized to produce a functionalizedphosphorous-containing monomer, and then the functionalizedphosphorous-containing monomer may be reacted with trimethoxysilane toproduce a phosphorous-containing silane monomer having the followinggeneric molecular structure:

wherein R₁, R₂ and R₃ are organic substituents (e.g., alkyl, aryl, etc.)that may be the same or different.

In general, a phosphorous-containing silane monomer in accordance withsome embodiments of the present invention includes two or moretrialkoxysilyl groups attached to an organic bridging group, wherein theorganic bridging group has a backbone portion that includes at least onephosphorous atom.

FIG. 1 is a block diagram illustrating an exemplary printed circuitboard (PCB) 100 having layers of dielectric material that incorporate abridged polysilsesquioxane-based flame retardant filler in accordancewith some embodiments of the present invention. In the embodimentillustrated in FIG. 1, the PCB 100 includes one or more module sites 105and one or more connector sites 110. FIG. 2 is a block diagramillustrating an exemplary laminate stack-up of the PCB 100 shown inFIG. 1. The configuration of the PCB 100 shown in FIG. 1 and itslaminate stack-up shown in FIG. 2 are for purposes of illustration andnot limitation.

As illustrated in FIG. 2, the laminate stack-up of the PCB 100 includesconductive planes (e.g., voltage planes 205 and signal planes 210)separated from each other by dielectric material 215. For example, thevoltage planes 205 include power planes P3, P5, P7, etc., while thesignal planes 210 include signal planes S1, S2, S4, etc. In accordanceto some embodiments of the present invention, one or more of the layersof the dielectric material 215 includes a bridgedpolysilsesquioxane-based flame retardant filler having bridgedpolysilsesquioxane particles that imparts flame retardancy.

Each layer of dielectric material (e.g., the dielectric material 215) ofa PCB typically includes a varnish coating (e.g., an FR4 epoxy resin, abismaleimide triazine (BT) resin, or a polyphenyleneoxide/trially-isocyanurate (PPO/TAIC) interpenetrating network) appliedto a glass fiber substrate (e.g., woven glass fiber) having its surfacemodified by a silane coupling agent (e.g., typically consisting of anorganofunctional group to bind to the varnish coating and a hydrolyzablegroup that binds to the surface of the glass fiber substrate, such asvinylbenzylaminoethylaminopropyl-trimethoxysilane ordiallylpropylisocyanurate-trimethoxysilane). In accordance with someembodiments of the present invention, a bridged polysilsesquioxane-basedflame retardant filler comprised of bridged polysilsesquioxaneparticles, for example, is incorporated into the varnish coating toimpart flame retardancy.

FIG. 3 is a block diagram illustrating an exemplary connector 300 havinga plastic housing 305 that incorporate a bridgedpolysilsesquioxane-based flame retardant filler in accordance with someembodiments of the present invention. In the embodiment illustrated inFIG. 3, the connector 300 is configured to make electrical contact withthe connector site 110 (shown in FIG. 1) of the PCB 100. Also in theembodiment illustrated in FIG. 3, the connector 300 includes a cable310. The configuration of the connector 300 shown in FIG. 3 is forpurposes of illustration and not limitation.

In accordance with some embodiments of the present invention, a bridgedpolysilsesquioxane-based flame retardant filler comprised of bridgedpolysilsesquioxane particles, for example, is incorporated into theplastic housing 305 to impart flame retardancy. The base material of theplastic housing 305 may be, for example, liquid crystal polymer (LCP) orany suitable thermoplastic or thermoset to which the filler is added.

One skilled in the art will appreciate that many variations are possiblewithin the scope of the present invention. Thus, while the presentinvention has been particularly shown and described with reference topreferred embodiments thereof, it will be understood by those skilled inthe art that these and other changes in form and details may be madetherein without departing from the spirit and scope of the presentinvention.

What is claimed is:
 1. An electronic circuit board, comprising: a laminate stack-up that includes a plurality of conductive planes separated from each other by a dielectric material, wherein the dielectric material includes a flame retardant filler comprising a bridged polysilsesquioxane prepared by sol-gel polymerization of a monomer comprising two or more trialkoxysilyl groups attached to an organic bridging group, wherein the bridging group contains a fire retardant group selected from a halogen atom, a phosphinate, a phosphonate, a phosphate ester, and combinations thereof.
 2. The electronic circuit board as recited in claim 1, wherein the bridging group contains at least two bromine atoms as the fire retardant group and the monomer is represented by the following formula:


3. The electronic circuit board as recited in claim 1, wherein the bridging group contains at least four bromine atoms as the fire retardant group and the monomer is represented by the following formula:


4. The electronic circuit board as recited in claim 1, wherein the bridging group contains a phosphinate as the flame retardant group and the monomer is represented by the following formula:

wherein R₁, R₂ and R₃ are organic substituents.
 5. A flame retardant filler, comprising: a bridged polysilsesquioxane prepared by sol-gel polymerization of a monomer comprising two or more trialkoxysilyl groups attached to an organic bridging group, wherein the organic bridging group has a backbone portion that includes at least two oxygen atoms, and wherein the organic bridging group is halogenated.
 6. The flame retardant filler as recited in claim 5, wherein the monomer is represented by the following formula:


7. The flame retardant filler as recited in claim 5, wherein the monomer is represented by the following formula:


8. A flame retardant filler, comprising: a bridged polysilsesquioxane prepared by sol-gel polymerization of a monomer comprising two or more trialkoxysilyl groups attached to an organic bridging group, wherein the organic bridging group has a backbone portion that includes at least one phosphorous atom.
 9. The flame retardant filler as recited in claim 8, wherein the monomer is represented by the following formula:

wherein R₁, R₂ and R₃ are organic substituents.
 10. A method of making a flame retardant filler, comprising the steps of: providing a monomer comprising two or more trialkoxysilyl groups attached to an organic bridging group, wherein the bridging group contains a fire retardant group selected from a halogen atom, a phosphinate, a phosphonate, a phosphate ester, and combinations thereof; preparing a bridged polysilsesquioxane by reacting the monomer in a sol-gel polymerization.
 11. The method as recited in claim 10, wherein the bridging group of the monomer contains at least two bromine atoms as the fire retardant group and the monomer is represented by the following formula:


12. The method as recited in claim 10, wherein the bridging group of the monomer contains at least four bromine atoms as the fire retardant group and the monomer is represented by the following formula:


13. The method as recited in claim 10, wherein the bridging group of the monomer contains a phosphinate as the flame retardant group and the monomer is represented by the following formula:

wherein R₁, R₂ and R₃ are organic substituents.
 14. An article of manufacture, comprising: a housing comprising a plastic material, wherein the plastic material includes a flame retardant filler comprising a bridged polysilsesquioxane prepared by sol-gel polymerization of a monomer comprising two or more trialkoxysilyl groups attached to an organic bridging group, wherein the bridging group contains a fire retardant group selected from a halogen atom, a phosphinate, a phosphonate, a phosphate ester, and combinations thereof.
 15. The article of manufacture as recited in claim 14, wherein the article of manufacture is a connector.
 16. The article of manufacture as recited in claim 14, wherein the bridging group contains at least two bromine atoms as the fire retardant group and the monomer is represented by the following formula:


17. The article of manufacture as recited in claim 14, wherein the bridging group contains at least four bromine atoms as the fire retardant group and the monomer is represented by the following formula:


18. The article of manufacture as recited in claim 14, wherein the bridging group contains a phosphinate as the flame retardant group and the monomer is represented by the following formula:

wherein R₁, R₂ and R₃ are organic substituents. 